WO2012127902A1 - Spectromètre de masse et source d'ions utilisée pour celui-ci - Google Patents

Spectromètre de masse et source d'ions utilisée pour celui-ci Download PDF

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Publication number
WO2012127902A1
WO2012127902A1 PCT/JP2012/051822 JP2012051822W WO2012127902A1 WO 2012127902 A1 WO2012127902 A1 WO 2012127902A1 JP 2012051822 W JP2012051822 W JP 2012051822W WO 2012127902 A1 WO2012127902 A1 WO 2012127902A1
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Prior art keywords
electrode
needle
sample
mass spectrometer
ion source
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Ceased
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PCT/JP2012/051822
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English (en)
Japanese (ja)
Inventor
宏之 佐竹
長谷川　英樹
益之 杉山
橋本　雄一郎
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Hitachi High Tech Corp
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Hitachi High Technologies Corp
Hitachi High Tech Corp
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Priority to US14/001,711 priority Critical patent/US8941060B2/en
Priority to EP12760440.3A priority patent/EP2688086B1/fr
Priority to CN201280007364.1A priority patent/CN103339708B/zh
Publication of WO2012127902A1 publication Critical patent/WO2012127902A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/165—Electrospray ionisation

Definitions

  • the present invention relates to a mass spectrometer and an ion source used therefor.
  • a liquid chromatograph mass spectrometer (LC / MS) is widely used for analyzing biological samples.
  • LC / MS liquid chromatograph mass spectrometer
  • gaseous ions are generated from the sample liquid separated by LC and introduced into the mass spectrometer.
  • a spray ionization method using an electrospray ionization (ESI) method is widely used.
  • ESI electrospray ionization
  • a capillary that is a pipe having an inner diameter of about several ⁇ m to several hundreds ⁇ m is usually used.
  • This electrospray ionization is performed at atmospheric pressure, and a high voltage is applied between the sample liquid at the end of the capillary piped to the LC and the counter electrode (mass analyzer inlet), and charged droplets are formed by the electrostatic spray phenomenon. Generate. The generated charged droplets are evaporated and gaseous ions are generated. The smaller the size of the initially generated charged droplet and the higher the charge amount, the higher the efficiency of generating gaseous ions.
  • nanoelectrospray in which the inner diameter of a capillary used for sample introduction is reduced from about 100 ⁇ m to about 1 to 2 ⁇ m, has been implemented. With this nanoelectrospray, it is possible to measure a very small volume of sample for a long time, and it has become possible to analyze a small amount of biomolecules.
  • Patent Document 1 Patent Document 2, and Non-Patent Document 1 disclose ionization methods using a needle.
  • a movable auxiliary needle is contained in a flow path in a pipe through which a sample in a capillary flows, and the auxiliary needle is vibrated and moved to supply a sample to a sampling needle at an opposing position.
  • An ionization method is described.
  • Patent Document 2 and Non-Patent Document 1 describe an ionization method in which a sample (probe) vibrates up and down between an origin position and a sample to perform sample attachment (sampling) and ionization.
  • Patent Document 1 discloses an electrospray method using an auxiliary needle.
  • a liquid sample flows in a capillary in the same manner as in a conventional electrospray, the inside of a capillary depends on the sample as in the conventional case. There are problems such as clogging and contamination.
  • Patent Document 2 discloses an ionization method in which a sample solution is attached to the surface of a needle, unlike a conventional electrospray.
  • the needle is vibrated up and down, and sampling and ionization are performed alternately (hereinafter referred to as an ionization method in which the needle is vibrated). Since the needle is used, the problem of clogging the sample in the capillary pipe and the problem of dirty pipe are solved. In this example, since it is only necessary to clean the surface of the needle to which the sample adheres, cleaning is easier than before.
  • FIG. 2A shows the movement of the needle of the ion source of the conventional example and the change of the ion intensity detected by the detector with respect to time.
  • the movement oscillating up and down is represented by a graph with the horizontal axis representing time and the vertical axis representing position, the movement becomes a sine wave as shown in the upper part of FIG. 2A.
  • the sample adheres when the needle is at the bottom and is ionized when the needle passes in front of the top mass analysis inlet.
  • FIG. 2A the timing at which ions are introduced into the mass spectrometer from the introduction port is shown surrounded by a broken line.
  • the lower part of FIG. 2A shows the change of the ion amount with respect to the time at that time.
  • the needle is separated from the introduction port and is not ionized because no discharge occurs.
  • This movement of the needle is problematic because it shows the same change in ion intensity over time even when it is represented by a rectangular wave instead of a sine wave.
  • the needle since the needle alternately repeats sampling and ionization of the sample, the sample is not continuously introduced but intermittently and intermittently introduced. For this reason, compared to electrospray using a capillary, the ionization method in which the needle is vibrated has a problem that the throughput of analysis is reduced.
  • Measures to reduce the throughput can be easily considered by increasing the speed of the needle drive unit and increasing the needle vibration frequency, that is, the needle movement speed.
  • the needle movement speed By making the needle move faster, it is possible to increase the number of times the needle comes before the inlet, that is, the number of times of ionization.
  • the ionization time itself is shortened, so that the ion amount itself is expected to decrease.
  • the needle passes through the vicinity of the inlet at a higher speed than before, it is expected that ionization becomes unstable and ionization is less likely to occur.
  • the liquid sample is shaken off by the high-speed motion, and ionization is not performed. For this reason, the problem cannot be solved by simply vibrating the needle at high speed.
  • the second problem is a decrease in quantitative accuracy.
  • the strength of the ionic strength is generated.
  • FIG. 2A when the amplitude of the ion intensity increases with time and the density of the ion amount is generated, if the ion amount exceeding the detection upper limit value of the detector reaches a detector with a dense sample, Will be counted down, making accurate analysis impossible.
  • a TDC time-to-digital converter
  • ADC analog-to-digital converter
  • the mass spectrometer of the present invention includes an ion source, a mass analyzer having a counter electrode provided with an inlet for introducing an ionized sample, and a controller for controlling the ion source.
  • the ion source includes a sample holding unit for holding a sample, a sample transport electrode having a plurality of needle electrodes, a power source for applying a voltage between the sample transport electrode and the counter electrode, and a plurality of needle electrodes as a sample.
  • a driving unit that drives the sample transport electrode so as to pass through the holding unit and the introduction port in order.
  • the sample transport electrode includes a disk electrode that rotates around a rotation axis, and a plurality of the sample transport electrodes are arranged so that the tip of the disk electrode is substantially perpendicular to the counter electrode with respect to the surface of the disk electrode.
  • This needle electrode is provided, and the axial direction of the rotating shaft is directed in a direction substantially parallel to the ion flow introduced from the tip of the needle electrode into the introduction port.
  • the sample transport electrode includes a disk electrode that rotates around the rotation axis, and has a structure in which a plurality of needle electrodes are provided radially in the in-plane direction of the disk electrode, and the axial direction of the rotation axis is The direction is substantially perpendicular to the direction of ion flow introduced from the tip of the needle electrode into the introduction port.
  • the sample transport electrode includes a flat plate electrode that rotates around a rotation axis.
  • the flat plate electrode has a plurality of convex portions with sharp tips on the outer peripheral portion, and the convex portions constitute needle electrodes.
  • the axial direction of the rotating shaft is oriented in a direction substantially perpendicular to the direction of ion flow introduced from the tip of the needle electrode into the introduction port.
  • the problem of throughput reduction which has been a problem with the ionization method in which the needle is vibrated, is solved, and high-throughput analysis becomes possible.
  • the ion flow flows uniformly over time, ions can be detected efficiently, and analysis with high quantitative accuracy is possible.
  • the flowchart which shows another example of the method for optimizing a rotational speed.
  • Schematic which shows another Example of the ion source of this invention.
  • the cross-sectional schematic of a disk electrode Schematic which shows another Example of the ion source of this invention.
  • Schematic which shows another Example of the ion source of this invention Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention. Schematic which shows another Example of the ion source of this invention
  • FIG. 1A is a schematic diagram illustrating an example of a mass spectrometer including an ion source according to an embodiment of the present invention.
  • FIG. 1B is a schematic view of the sample transport electrode viewed from the mass spectrometer side.
  • Both electrospray ion sources using capillaries and electrospray ion sources using needle electrodes can operate at atmospheric pressure.
  • Sample ions ionized by electrospray in the ion source using the needle electrode of this embodiment are introduced into the mass analyzer 20 from the inlet 21.
  • the sample ions introduced into the mass spectrometer 20 pass through the ion guide 23 of the differential evacuation unit and are analyzed by a mass analyzer such as a quadrupole mass filter 24.
  • the ion source of the present embodiment includes a sample transport electrode 7 in which a needle electrode 1 made of a conductor is mounted on a circular disk electrode 2 made of a conductor such as metal so as to stand vertically from the disk surface. Further, in order to prevent the sample solution 5 from adhering to the disc electrode 2 and being contaminated, a metal rod protrudes from the disc electrode 2 in the radial direction, and the needle electrode 1 is mounted on the tip. There is no metal rod, and the needle electrode 1 may be directly attached to the disc electrode 2. The needle electrode 1 faces the counter electrode 22, and the disk surface of the disk electrode 2 is disposed so as to face the counter electrode 22.
  • the sample transport electrode 7 including the needle electrode 1 and the disk electrode 2 is rotated by the drive unit 3 based on the control from the computer 31.
  • a voltage is applied from the high voltage power source 4 between the disc electrode 2 with the needle electrode 1 and the counter electrode 22.
  • a DC voltage of about 1 to 5 kV is applied.
  • An electrospray that applies an AC voltage instead of a DC voltage can be used similarly.
  • a container 6 such as a glass bottle containing the sample solution 5 is disposed in front of the inlet 21 of the mass spectrometer 20 so that the needle electrode 1 is immersed in the sample solution 5.
  • the sample transport electrode 7 rotates around the central axis of the disk.
  • the drive unit 3 uses, for example, a motor to control the rotation speed of the electrodes.
  • the introduction port 21 is positioned so as to face the needle electrode 1 and is disposed on a circumferential track through which the tip of the needle electrode 1 passes.
  • the introduction port 21 provided in the counter electrode 22 is discharged and ionized only when the portion of the introduction port 21 protrudes about several millimeters toward the needle electrode 1 and the needle electrode 1 comes near the introduction port 21. Is called.
  • the result monitored by the detection unit 25 is stored, analyzed, and displayed by the computer 31.
  • the computer 31 can control the rotational speed of the drive unit 3 and the high-voltage power supply 4 based on the data analysis result.
  • the shape of the needle electrode 1 is preferably such that the radius of curvature of the tip is sharply pointed to about several ⁇ m to several tens of ⁇ m, and discharge is likely to occur.
  • the material of the needle electrode 1 may be a conductive substance, for example, a metal such as aluminum, iron, copper, silver, gold, platinum, tungsten, nickel, a mixture (alloy) thereof, or stainless steel. It may be a needle shaped like a sewing needle used in sewing. If the needle electrode 1 is further provided with a plurality of fine, sharp projections having a radius of curvature of several ⁇ m or less so that the liquid can easily adhere, the sample solution 5 is easily held on the surface of the needle electrode. In the present invention, not only a needle having a shape like a sewing needle, but also all of the metal tip having a sharp radius of curvature of about several ⁇ m to several tens of ⁇ m are defined as needle electrodes.
  • the number of needle electrodes 1 may be about 3 to 10. For example, if there are eight as shown in FIG. 1B, sufficient ionization can be performed at a frequency of 8 times / second even if the rotation speed of the sample transport electrode 7 is as low as 1 rotation / second.
  • FIG. 2B shows the movement of the needle electrode of the ion source and the time variation of the ion intensity detected by the detector in this example.
  • the ion intensity is monitored by the detection unit 25
  • the ion current can be monitored by the counter electrode 22 or an electrode of another mass analysis unit.
  • the sample transport electrode 7 is rotated using a motor, the height position of the needle electrode 1 with respect to time can be drawn as a sine wave as in FIG. 2A.
  • FIG. 2A shows that, in this embodiment, since there are a plurality of needle electrodes 1, a sine wave line is drawn by the number of needles.
  • each sample electrode 1 is attached to the needle electrode 1, ionization is sequentially performed at the timing of passing through the illustrated inlet 21.
  • the rotational speed can be made slower than in the prior art, and the period of the sine wave can be increased as shown in the figure.
  • the frequency at which the needle electrode reaches the introduction port can be easily increased, and the passing speed of the needle electrode can be reduced by adjusting the interval between the needle electrodes to be arranged, so that stable ionization can be achieved. Is possible. Furthermore, there is no need for a driving unit such as a motor that requires a large amount of electric power at high speed, and a small and inexpensive driving unit is sufficient.
  • the rotation speed of the sample transport electrode 7 needs to be optimized. This is because the optimum ionization conditions may change each time the analysis sample, solvent, and needle electrode change. When the rotation speed is slow, there arises a problem that the sample solution 5 is dried, and ions are intermittently introduced into the mass spectrometer as shown in FIG. By increasing the rotation speed, the peak value of the ionic strength when each needle electrode passes through the introduction port decreases, but the needle electrode passes immediately in front of the introduction port from one to the next, As shown in FIG. 2B, the ionic strength approaches the uniform strength in time and is close to a continuous flow. This is because the next needle electrode reaches the inlet before the ionic strength of the previous needle electrode is attenuated.
  • the rotational speed is too high, the ionic strength decreases due to problems such as the sample not attaching to the needle electrode or the sample blowing off by centrifugal force. Furthermore, if the speed at which the needle electrode passes in front of the introduction port is too fast, the ionization discharge becomes unstable, and the discharge (ionization) time is shortened, so that the ionic strength is lowered. For this reason, it is necessary to optimize the rotation speed.
  • FIG. 3 is a flowchart showing an example of a method for optimizing the rotation speed.
  • the sample solution 5 is put in the container 6 and placed in front of the inlet 21 of the mass spectrometer 20 (S11).
  • the center rotational speed A, the swing width a, the number n of measurement points, and the time t to be measured are determined and input to the computer 31 (S12).
  • A 3 rotations / second
  • a 1 rotation / second
  • n 3 points
  • the ion intensity is measured at three rotation speeds of 2, 3, and 4 rotations / second.
  • the time t is a measurement time and may be longer than the rotation period.
  • the computer first sets the rotation speed to 2 times / second (S13).
  • the computer applies a high voltage to the needle electrode 1 via the disk electrode 2 (S14), and controls the drive unit 3 according to the setting, and the drive unit 3 rotates the sample transport electrode 7 with the needle electrode (S15). .
  • the sample solution is ionized (S16).
  • the detector detects ions for a measurement time of 3 seconds (S17).
  • the ions to be measured may be only ions of a certain m / z, or the amount of ions of all ions may be monitored.
  • the computer calculates the dispersion value (variation) of the ionic strength of the measurement data for 3 seconds (S18).
  • the dispersion value may be a standard deviation with respect to the average value of ionic strength over 3 seconds. By reducing this dispersion value, it is possible to avoid the state where the ionic strength has strong and weak unevenness as shown in FIG. 2A and to find a condition that is uniform in time as shown in FIG. 2B.
  • the analysis may be performed by a computer during the next measurement. Subsequently, the rotational speed of the drive unit is controlled to 3 times / second (S19), and similarly, measurement is performed for 3 seconds.
  • the measured dispersion values at three points are compared, and when the dispersion value is minimized, the optimum point is determined, and the rotation speed at that time is determined as the optimum speed (S20).
  • the optimum rotation speed is set in the drive unit and driven (S21). Under this optimum rotational speed condition, this measurement is started for several seconds to several minutes (S22). This optimization is preferably performed fully automatically under computer control.
  • FIG. 4 is a flowchart showing another example of a method for optimizing the rotation speed.
  • the basic flow is the same as in the example of FIG.
  • the difference from FIG. 3 is that, in the analysis, not the dispersion value of the ion intensity but the area value (time integrated value) of the ion intensity is calculated and used as an optimization index (S18A). By maximizing the area value, ions can be collected most efficiently.
  • FIG. 5 is a flowchart showing another example of a method for optimizing the rotation speed.
  • the basic flow is the same as in the examples of FIGS.
  • the difference from the example shown in FIG. 3 and FIG. 4 is that, in the analysis, both the dispersion value and the area value of the ionic strength are calculated, and both are used as optimization indexes (S18B).
  • S18B optimization indexes
  • FIG. 6 is a flowchart showing another example of a method for optimizing the rotation speed.
  • the optimum point is roughly investigated by roughly rotating the rotation speed, and then the periphery of the optimum rotation speed is further examined and optimized.
  • the optimum is efficiently performed in a short time. You can find the rotation speed.
  • the basic flow is the same as the previous examples, but the left part is roughly measured by changing the rotational speed, and the middle part is a two-stage flow in which the rotational speed is measured finely.
  • the middle part is a two-stage flow in which the rotational speed is measured finely.
  • A 3 rotations / second
  • a 1 rotation / second
  • n 3 points
  • the rotation speed at which the area is maximum is 3 rotations / second
  • a flow for examining the periphery of the 3 rotations / second by further rotating the rotation number is shown in the middle part.
  • FIG. 7 is a flowchart showing another example of a method for optimizing the rotation speed. Similar to the example of FIG. 6, the method is to investigate the optimum point roughly by roughly swaying the rotational speed and then further investigate and optimize the periphery of the optimum rotational speed. In this example, the flow is continued until the maximum point of the area value of the ionic strength is found.
  • FIG. 8 is a graph showing the relationship between the movement position of the tip of each needle electrode and time, with time on the horizontal axis and position (height) on the vertical axis.
  • the disk electrode 2 is rotated 45 degrees, stopped for a fixed time, and intermittently moved 45 degrees using a stepping motor or the like.
  • the timing at which ions are introduced from the introduction port into the mass spectrometer is surrounded by a broken line.
  • one of the needle electrodes 1 is placed stationary in front of the inlet 21 and ionization is performed.
  • an ion guide ion guide
  • a quadrupole, an octopole, a hexapole, an ion A funnel may be provided instead of the ion guide.
  • the structure without an ion guide may be sufficient.
  • the mass spectrometer is also equipped with an ion trap, triple quadrupole mass spectrometer (triple quadrupole mass spectrometer), time-of-flight mass spectrometer (Time- of-flight mass spectrometer, magnetic mass spectrometer, orbitrap mass spectrometer, Fourier-transform mass spectrometer, Fourier-transform ion cyclotron resonance mass spectrometer (Fourier-transform ion cyclotron) resonance (mass / spectrometer) may be used.
  • the sample solution 5 attached to the needle electrode 1 is dried over time and is not ionized. In order to prevent the drying, it is desirable to ionize the sample solution 5 as soon as possible after adhering to the needle electrode 1.
  • the rotation direction of the disk electrode 2 with the needle electrode is preferably counterclockwise as shown by the arrow when viewed from the introduction port 21 side.
  • chamber of an ion source is humidified with water or a solvent with a humidification mechanism, drying of the sample solution 5 may be prevented. Further, it is desirable that water or a solvent is sprayed in the vicinity of the introduction port so that the sample solution attached to the needle electrode 1 is not dried.
  • the same high voltage as that of the needle electrode may be applied to the container 6 and the liquid sample 5. Also, it may be floated without being connected to potential anywhere (floating).
  • MALDI matrix-assisted laser desorption / ionization
  • FIG. 9 is a schematic diagram showing an example of the configuration of an ion source and a mass analyzer according to another embodiment of the present invention.
  • the electrospray using the needle electrode as in this example but also normal electrospray, and the ion strength decreases or becomes unstable due to deterioration such as accumulation or damage of impurities on the capillary or needle electrode. Become. For this reason, it is necessary to monitor the amount of ions periodically, and to replace or clean the needle electrode 1 when the amount of ions decreases or when the discharge is unstable and the ion intensity dispersion value increases.
  • a method for cleaning and replacing the needle electrode 1 and a method for determining the timing will be described.
  • the ion source of the present embodiment is the same as that of the first embodiment with respect to the rotation driving method, ionization / analysis method, monitoring method, and the like.
  • the plurality of containers 6 containing the sample solution 5 and the container 6 containing the cleaning liquid 10 are on the rotary stage 11 and the upper and lower stages 12 controlled by the computer 31. After the measurement of the sample solution in one container is completed, the rotary stage 11 and the upper and lower stages 12 are driven by a command from the computer 31 and the needle electrode 1 is immersed in the container 6 containing the cleaning liquid 10. The needle electrode 1 is washed by rotating the sample transport electrode 7 in this state. At the same time, it is better to vibrate the cleaning liquid 10 in the manner of an ultrasonic cleaning machine.
  • the cleaning liquid 10 may be ethanol, acetone, methanol, a sample dilution solvent, or the like.
  • Cleaning is performed for a time determined by the user, from a few seconds to a few minutes.
  • the discharge current flowing from the tip of the needle electrode 1 to the counter electrode 22 is monitored, and the difference is determined as compared with a new needle electrode. That is, when the needle tip of the needle electrode is contaminated with impurities, it is difficult to discharge and the discharge current is reduced.
  • the threshold value is determined to be, for example, 80% of the discharge current at the time of a new product, and cleaning is continued until the discharge current recovers to the threshold value or more.
  • a method of increasing the voltage of the high-voltage power supply 4 may be used. Increasing the voltage may restore the discharge current and ionization.
  • the voltage of the high-voltage power source may be increased by 100 V, for example, until the discharge current recovers.
  • the replacement of the needle electrode 1 is necessary because ionization is hindered due to unavoidable accumulation of impurities on the needle tip and deterioration of the needle tip shape.
  • the timing for exchanging the needle electrode 1 is when the threshold ionic strength is not reached even when the voltage of the high-voltage power supply 4 is raised, that is, when the discharge current is not recovered even if the power supply voltage is raised even after cleaning.
  • the sample transport electrode 7 is replaced with a new one, the discharge current is measured again, and after confirming that there is no problem, the measurement of the next sample is started.
  • the monitoring for determining the cleaning and replacement timing of the needle electrode 1 may be performed by monitoring not the discharge current but the amount of ions ionized using a standard sample with a detector.
  • determination may be made by observing the needle tip with a microscope after washing and checking for impurities. This can be determined directly by observing with a microscope. If dirt appears, wash again.
  • Example 3 10A to 10F are schematic views showing another embodiment of the ion source of the present invention.
  • a plurality of needle electrodes 1 were provided on the peripheral edge of the disk electrode 2, and the tip of each needle electrode 1 was oriented in a direction perpendicular to the surface of the disk electrode 2.
  • a plurality of needle electrodes 1 are provided radially on the disk electrode 2.
  • the axial direction of the rotation axis of the disk electrode 2 is substantially parallel to the flow direction of the ion flow generated from the tip of the needle electrode and introduced into the introduction port in the first embodiment. The direction is substantially perpendicular to the direction of ion flow.
  • FIG. 10A shows an ion source using a sample transport electrode 8 having a needle electrode 1 made of a conductor in the radial direction of a circular disk electrode 2 made of a conductor such as metal, as in the case of the first embodiment.
  • the shape of the needle electrode 1 and the disk electrode 2 is the same as that of the first embodiment, but the attachment direction of the needle electrode 1 with respect to the disk electrode 2 is different. Further, the posture of the sample transport electrode 8 with respect to the mass spectrometer is different from that of the first embodiment. In this embodiment, the rotation direction of the disk electrode 2 is 90 degrees different from that of the first embodiment. However, when the disk electrode 2 rotates, the plurality of needle electrodes 1 are sequentially positioned at the introduction port 21 of the counter electrode 22. Similarly, the sample solution adhering to the needle electrode is ionized. A voltage is applied to the needle electrode 1 through the disk electrode 2 using a high voltage power source 4.
  • a container 6 such as a glass bottle containing the sample solution 5 is disposed in front of the inlet 21 of the mass spectrometer 20 so that the needle electrode 1 is immersed in the sample solution 5.
  • the disc electrode 2 provided with the needle electrode 1 is arranged in such a manner that the inlet 21 of the mass analyzing unit overlaps the rotation plane.
  • the drive unit 3 rotates the sample transport electrode 8.
  • the rotation direction should be rotated counterclockwise as shown by the arrow in order to shorten the time from sample attachment to ionization.
  • the high voltage is also applied to the needle electrode 1 through the disk electrode 2 by the high voltage power source 4 as in the first embodiment.
  • the optimization of the number of needle electrodes 1 and the rotation speed is the same as in the case of the first embodiment.
  • FIG. 10B shows an example in which the inlet 21 and the counter electrode 22 are arranged above the sample transport electrode 8. Even in this case, the sample solution can be ionized as in FIG. 10A.
  • the method of applying a high voltage to the sample transport electrode 8 from the high voltage power source 4 and rotating the sample transport electrode 8 by the driving unit 3 is the same as in the case of the first embodiment and FIG. 10A.
  • FIG. 10C shows an example in which the rotation surface of the disk electrode 2 constituting the sample transport electrode 8 is tilted from the vertical direction. Even if the rotation surface is tilted, the sample solution adhering to the needle electrode 1 can be ionized and introduced into the mass spectrometer from the inlet 21.
  • the method of applying a high voltage to the sample transport electrode 8 from the high-voltage power source 4 and rotating the sample transport electrode 8 by the driving unit 3 is the same as that of the first embodiment and the example of FIG. 10A.
  • FIG. 10D is a schematic view showing an example in which the plate electrode 9 is used as the sample transport electrode.
  • a plurality of convex portions were provided on the outer peripheral portion of the plate electrode 9 made of a conductor, and the tip of the convex portion was sharply processed like a needle tip. Even if it is not an elongated shape like a literal needle, if the tip is sharp like this, an electric discharge phenomenon occurs due to discharge, and ionization is performed.
  • a convex portion capable of electrostatic spraying in which the outer peripheral portion of the flat plate electrode is processed into a star shape and the tip is sharpened, is also referred to as a needle electrode.
  • the method of applying a high voltage from the high-voltage power supply 4 to the flat electrode 9 and rotating it by the drive unit 3 is the same as in the case of the first embodiment and the example of FIG. 10A.
  • FIG. 10E is a schematic diagram showing an example of an ion source using a disk electrode 16 having a sharp tip made of a conductor such as metal as a sample transport electrode.
  • the disc electrode 16 is not pointed like a needle but has a thin tip at the outer periphery of the disc electrode 16 like a cutter knife blade as shown in the schematic sectional view of FIG. 10F. It has a pointed shape.
  • the radius of curvature of the tip is sharply pointed to about 1 ⁇ m to several tens of ⁇ m. As described above, even if the sharp portion is not in the form of dots but is distributed in a line shape like a knife blade, an electrostatic spray phenomenon occurs from the blade portion.
  • the blade-like structure formed along the circumferential direction on the outer periphery of the disk electrode is also referred to as a needle electrode.
  • This needle electrode can be considered to be an infinite number of small needle electrodes in the circumferential direction of the disk electrode.
  • the method of applying a high voltage to the disk electrode 16 from the high-voltage power supply 4 and rotating the disk electrode 16 by the driving unit 3 is the same as that of the first embodiment and the example of FIG. 10A.
  • Example 4 11A to 11G are schematic views showing another embodiment of the ion source of the present invention.
  • the sample solution adhered to the needle electrode is transported to the inlet of the counter electrode by rotating the sample transport electrode, but in this embodiment, the sample transport electrode is moved back and forth to the needle electrode. The adhered sample solution is transported to the inlet of the counter electrode.
  • FIG. 11A shows an embodiment of an ion source using a sample transport electrode 17 having a structure in which a plurality of needle electrodes 1 made of a conductor are attached to a rod-like electrode 15 made of a conductor.
  • a high voltage is applied from the high voltage power source 4 to the needle electrode through the rod-shaped electrode 15.
  • the drive unit 3 drives the rod-like electrode 15 to reciprocate up and down.
  • the sample transport electrode 17 is provided with a plurality of needle electrodes 1 and is arranged so that all the needle electrodes are immersed in the sample solution 5 in the container 6 when located at the lowermost part. Moreover, when located in the uppermost part, it is good to arrange
  • FIG. 11B shows an example in which the tip of the needle electrode 1 faces downward in the material transport electrode shown in FIG. 11A.
  • FIG. 11C is an example in which each needle electrode is bent in an upward chevron shape further inclined with respect to the example of FIG. 11B.
  • the sample solution 5 attached to the needle electrode 1 on the right side of the apex is tilted in two steps so that the apex of the peak is formed between the connection portion of the needle electrode 1 to the rod-shaped electrode 15 and the tip of the needle electrode.
  • the sample solution 5 adhering to the left side and the sample solution 5 adhering to the rod-like electrode 15 flow to the left side.
  • the sample solution 5 is not supplied from the rod-shaped electrode 15 to the needle electrode 1, but since almost the same amount of sample can be supplied to the needle tip to any of the plurality of needle electrodes 1, it is ionized in a stable and constant amount. Suitable for quantitative measurement.
  • FIG. 11D is an example in which fine grooves 18 are dug in the surface of the needle electrode 1.
  • the left figure of FIG. 11D is a schematic plan view of one needle electrode, and the right figure is a schematic sectional view thereof.
  • the groove 18 has a depth and a width of about several ⁇ m to several tens of ⁇ m, and one or a plurality of grooves are cut toward the needle tip. According to such a structure, since the sample solution 5 is stored in the groove 18, a large amount of sample can be attached to and held on the needle electrode. In addition, the sample can be smoothly supplied to the tip of the needle through the groove 18. You may provide a groove
  • FIG. 11E is an enlarged view of the tip portion of the needle electrode, and shows an example in which the protrusion 19 is provided on the needle electrode 1. If there are a plurality of small protrusions 19 as shown in the figure, a large number of samples adhere to the protrusions, and a large amount of sample solution can be supplied.
  • the needle electrode described in Examples 1, 2, and 3 may be provided with a protrusion as in this example.
  • FIG. 11F shows an example of a needle electrode 1 having a shape that can hold a liquid like a spoon and having a sharp tip and ionization. By allowing the liquid to flow from the tray little by little to the tip, the sampling frequency of the sample can be reduced, thus enabling efficient measurement.
  • the needle electrodes described in Examples 1, 2, and 3 may have a shape as in this example.
  • FIG. 11G is a schematic view showing an example of an ion source using two needle electrodes 1 made of a conductor as a sample transport electrode.
  • the two needle electrodes 1a and 1b are moved up and down at a phase different by 180 degrees by the drive unit 3. That is, when one needle electrode 1a is positioned at the lowermost portion, the other needle electrode 1b is alternately operated so as to be positioned at the uppermost portion.
  • Two needle electrodes may be vertically moved and moved up and down, but by arranging the needle electrodes obliquely as shown in FIG. 11G, both of the two needle electrodes 1a and 1b are in the center of the introduction port 21.
  • the sample solution can be ionized efficiently.
  • the two needle electrodes 1a and 1b can sample the same sample solution 5.
  • the two needle electrodes can be driven by one drive unit 3, but an independent drive unit 3 may be provided for each of the two needle electrodes.
  • a high voltage is supplied to the two needle electrodes 1a and 1b from the same high-voltage power supply 4 so that no discharge occurs between the needle electrodes.
  • Example 5 12A to 12D are schematic diagrams showing another embodiment of the ion source of the present invention.
  • the sample is a solid sample or a solid sample.
  • FIG. 12A shows an embodiment in which the sample is changed to a solid sample in the embodiment shown in FIG. 10A. Since the sample is solid, the solid sample 51 can be adsorbed and held on a horizontally oriented sample stage 52 as shown in the figure. For this reason, the degree of freedom of the device configuration is increased. Further, the sample stage 52 may be arranged at the top, and the sample may be held downward. As in the case of Example 3 in which the sample described so far is a liquid sample, a high voltage is applied to the disc electrode 2 with the needle electrode 1 by the high voltage power source 4, and the sample transport electrode 8 is rotated by the drive unit 3. To drive.
  • FIG. 12B shows an example in which a cleaning function is further added to the embodiment of FIG. 12A.
  • the cleaning liquid 10 is installed below the sample transport electrode 8 with the needle electrode 1, and the needle electrode 1 is immersed and cleaned in the cleaning solution when passing near the bottom.
  • the needle electrode 1 is cleaned by passing through the cleaning liquid 10 immediately after the sample adhesion and ionization measurement.
  • the problem that the needle electrode 1 becomes dirty and cannot be washed with time after the sample has adhered is avoided, so that the life of the needle electrode 1 can be extended and the replacement frequency of the needle electrode 1 can be reduced. It becomes possible to reduce.
  • FIG. 12C shows an example in which the positions of the sample stage 52 and the introduction port 21 are different.
  • the sample may be provided at any position as long as it can touch the tip of the needle electrode 1.
  • the position of the introduction port 21 may be any position as long as it is near the tip of the needle electrode 1.
  • FIG. 12D is an example where the sample is solid in Example 1. Also in this example, by disposing the cleaning liquid 10 below the sample transport electrode 8, ionization of the solid sample 51 and cleaning of the needle electrode 1 can be alternately repeated.
  • Example 6 13A to 13E are schematic views showing another embodiment of the ion source of the present invention.
  • the sample is supplied by liquid spray or liquid pipe supply.
  • FIG. 13A shows an example of an ion source in which the sample solution supply method is changed to spraying and a cleaning function is added in the configuration example shown in the first embodiment.
  • the sample supply pipe used for spraying has a double cylindrical structure, the liquid sample 5 passes through the center sample pipe 41, and the nebulizer gas 42 flows through the surrounding gas pipe 43.
  • the sample pipe 41 is a pipe having an inner diameter of several tens of ⁇ m to several hundreds of ⁇ m, and the sample solution 5 is sprayed by the nebulizer gas 42 to attach the liquid sample to the needle electrode 1.
  • the nebulizer gas 42 nitrogen, air, or the like is used. Although the spraying is performed from above in the figure, it may be performed from the lateral direction.
  • the needle electrode 1 is cleaned in the same manner as in the second embodiment.
  • a container containing the cleaning liquid 10 is disposed below the sample transport electrode 7 and is cleaned each time the needle electrode 1 passes through the cleaning solution.
  • the sample transport electrode 7 makes one round, the attachment of the sample to the needle electrode 1 by spraying, the ionization of the sample, and the cleaning of the needle electrode 1 are repeated.
  • the sample pipe 41 used for spraying is disposable or cleaned for each sample.
  • the sample pipe 41 is cleaned by passing a cleaning liquid through the sample pipe 41 for about several seconds to several minutes. Therefore, it is preferable to prepare a plurality of sample pipes 41 and to wash other sample pipes during the measurement.
  • a high voltage is applied from the high voltage power source 4 to the disk electrode 2 with the needle electrode 1, and the drive unit 3 rotates the drive.
  • FIG. 13B is a diagram illustrating an example in which the nebulizer gas is not used in FIG. 13A.
  • the sample solution 5 becomes spherical due to surface tension at the tip of the sample pipe 41, and the sample adheres to the needle electrode 1 when the needle electrode 1 passes so as to contact the spherical portion.
  • the sample supply pipe can be attached to the needle electrode from above or from the side. Also in this example, the needle electrode 1 is cleaned by the cleaning liquid 10 every time the sample transport electrode 7 makes one round as in the previous example.
  • FIG. 13C is a diagram showing an example in which the sample solution 5 is directly supplied to the needle electrode 1 from the hole opened in the lower part of the container containing the sample solution 5.
  • the sample solution 5 can be supplied by tilting the container. At that time, the sample solution 5 leaking from the hole of the container may be transmitted to a thin thread-like member to supply the sample solution 5 to the needle electrode 1.
  • FIG. 13D is a diagram showing an example in which the sample transport electrode 8 is configured by the disc electrode 2 with the needle electrode 1 as shown in FIG. 10A.
  • Example 3 is the same as Example 3 except that the sample is supplied by spraying.
  • the sample supply method can be implemented by the type shown in FIGS. 13B and 13C.
  • the direction of spraying may be spraying in the direction of the rotational axis or spraying from an oblique direction.
  • FIG. 13E is a diagram showing an example in which the introduction port 21 of the counter electrode 22 is below the sample transport electrode 7 and the needle electrode 1 faces downward.
  • the operation method is the same as in FIG. 13A.
  • Example 7 14A to 14C are schematic views showing another embodiment of the ion source of the present invention.
  • This embodiment is an embodiment in a form in which there are a plurality of sample introduction ports in the mass spectrometer.
  • the ion transmission efficiency can be improved. Therefore, in this embodiment, a trajectory for moving the needle electrodes is set so that all the needle electrodes can sequentially pass in front of all the introduction ports.
  • a description will be given by taking a mass spectrometer having five sample inlets as an example, but the present embodiment can also be applied to cases where the number of inlets is other than five.
  • FIG. 14A is a schematic front view of the ion source of the present embodiment
  • FIG. 14B is a schematic diagram showing the relationship between the ion source and the mass analysis unit.
  • the sample transport electrode of this embodiment is composed of a string-like electrode 53 made of a conductor and a plurality of needle electrodes 1 attached to the electrode 53.
  • the plurality of needle electrodes 1 are attached to a string-like electrode 53 made of a conductor so that the tip faces the direction of the introduction port 21 of the mass spectrometer, and the string-like electrode made of the conductor is attached.
  • the electrode 53 moves along a predetermined trajectory.
  • the needle electrode 1 is immersed in the sample solution in the container at the bottom of the track, where the sample solution 5 adheres to the needle electrode 1 and passes in front of the five inlets in the vicinity of the top of the track in order. When reaching before 21, the sample solution is ionized.
  • the string-like electrode 53 made of a conductor may be, for example, a metal chain. Other operations are the same as those in the first embodiment.
  • FIG. 14C shows an example using the supply method in which the container containing the cleaning liquid 10 is placed below the sample transport electrode and the sample described in Example 6 is sprayed.
  • sample spraying, ionization, and cleaning are repeated as described in the sixth embodiment.
  • Other operations are the same as those in the first embodiment and FIG. 14A.
  • the capillary pipe is clogged or contaminated.
  • the efficiency of the ion source is improved, and high-throughput analysis is possible.
  • the ion flow flows uniformly over time, analysis with high quantitative accuracy becomes possible.
  • a stable ion source and a small and inexpensive ion source can be provided.
  • this invention is not limited to the above-mentioned Example, Various modifications are included.
  • the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described.
  • a part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment.
  • the needle electrode is described as a specific example of a metal needle made of a conductor, but the needle electrode is not limited to a conductor such as a metal, and may be a substance other than a conductor. Good. For example, paper, wood, plastic, glass, silicon, other porous materials, and materials that hold and adsorb liquid can be used. Even if the needle electrode is a substance other than a conductor, if a sample solution or solvent is attached to and held on the needle electrode, a high voltage is applied through the sample solution or solvent and ionization is possible. Also in a needle electrode made of paper, wood, etc., it is desirable that the tip is sharply pointed because discharge becomes easier and discharge becomes stable.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

La présente invention vise à améliorer la précision de détermination d'analyse sans réduire la plage dynamique pour la mesure de concentration, par réalisation d'une ionisation stable par électropulvérisation, etc., qui répète un échantillonnage et une ionisation à l'aide d'une électrode à aguille mobile. Une tension est appliquée à partir d'une source d'alimentation haute tension (4) à une électrode de transport d'échantillon (7) ayant une pluralité d'électrodes à aiguille (1), et un dispositif d'entraînement (3) entraîne en rotation l'électrode de transport d'échantillon (7). La pluralité d'électrodes à aiguille (1) auxquelles adhère la solution échantillon (5) se déplacent en séquence vers l'entrée (21) d'un spectromètre de masse (20), des ionisations par électropulvérisation étant ainsi effectuées de manière successive.
PCT/JP2012/051822 2011-03-18 2012-01-27 Spectromètre de masse et source d'ions utilisée pour celui-ci Ceased WO2012127902A1 (fr)

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EP12760440.3A EP2688086B1 (fr) 2011-03-18 2012-01-27 Spectromètre de masse et source d'ions utilisée pour celui-ci
CN201280007364.1A CN103339708B (zh) 2011-03-18 2012-01-27 质量分析装置及其使用的离子源

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WO2020170335A1 (fr) * 2019-02-19 2020-08-27 株式会社島津製作所 Spectromètre de masse
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EP2688086A1 (fr) 2014-01-22
US8941060B2 (en) 2015-01-27
JP2012199027A (ja) 2012-10-18
CN103339708A (zh) 2013-10-02
US20130334416A1 (en) 2013-12-19
CN103339708B (zh) 2015-12-23
EP2688086A4 (fr) 2015-04-29
JP5632316B2 (ja) 2014-11-26

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